CN113214795A - Preparation method of ionic liquid phase-change microcapsule - Google Patents
Preparation method of ionic liquid phase-change microcapsule Download PDFInfo
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- CN113214795A CN113214795A CN202110085100.9A CN202110085100A CN113214795A CN 113214795 A CN113214795 A CN 113214795A CN 202110085100 A CN202110085100 A CN 202110085100A CN 113214795 A CN113214795 A CN 113214795A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Abstract
The invention relates to a preparation method of a phase-change microcapsule coated with ionic liquid, belonging to the technical field of novel phase-change functional materials and preparation. The wall material of the ionic liquid phase-change microcapsule is a polymer with excellent chemical stability, thermal conductivity, mechanical property and high temperature creep resistance, and the core material is ionic liquid with phase-change heat storage performance and various types. The ionic liquid has the advantages of wide liquid range, large heat capacity, excellent thermal and chemical stability and the like, and is one of ideal media of the existing phase-change heat storage material. The phase-change ionic liquid is sealed in the spherical capsule, so that the mass transfer contact area can be increased, the loss of the ionic liquid is avoided, the multiple cyclic utilization of the ionic liquid phase-change material is realized, and the application field of the ionic liquid in the phase-change heat storage technology is widened.
Description
Technical Field
The invention relates to a method for preparing a phase change energy storage material by utilizing a microcapsule technology, in particular to a technology for surface coating of an ionic liquid phase change heat storage material, which can realize the production of phase change materials with different phase change temperatures.
Background
The ionic liquid is a salt which is composed of organic cation and inorganic or organic anion and is liquid at room temperature or near room temperature. Compared with the traditional phase change energy storage material, the ionic liquid as the phase change energy storage material has the following advantages: (1) the melting point of the ionic liquid has strong designability, and corresponding structural adjustment can be made according to the target phase transition temperature; (2) the organic energy storage material has good thermal stability and higher decomposition temperature, is higher than the prior organic energy storage material, can not be decomposed or generate other changes after being subjected to multiple phase change cycles, and is suitable for being used as a heat storage material of a high-grade heat source; (3) the pH is controllable, and the excellent pH adjustability of the ionic liquid is beneficial to forming a multi-component system with other substances with higher requirements on the pH environment; (4) the density of the ionic liquid is stable and easy to adjust, and the density of the ionic liquid is stable in different environments and is not influenced by factors such as temperature, humidity and the like. (5) The hydrophilicity and hydrophobicity are adjustable, and an oil-in-water or water-in-oil system can be formed according to the microcapsule preparation method. Therefore, the wide liquid range, large heat capacity and excellent thermal and chemical stability of the ionic liquid are one of the ideal media of the existing heat storage materials.
Because the phase change process of the ionic liquid is easily influenced by impurities (such as water, absorbed gas and the like), the development of a functional material which not only has the phase change advantage of the ionic liquid but also can improve the phase change stability of the ionic liquid has important significance for the application of the ionic liquid in the aspect of heat storage. The ionic liquid phase-change microcapsule technology is characterized in that the microcapsule technology is applied to the preparation of ionic liquid phase-change materials, phase-change ionic liquid is sealed in spherical capsules, the phase-change advantage of the ionic liquid is kept, the loss of the ionic liquid is prevented, and the problem of phase-change stability of the ionic liquid is solved, so that the application performance of the ionic liquid phase-change materials is improved, and the application field of the phase-change heat storage technology is widened.
Description of the drawings:
FIG. 1 is an electron microscope image of 1-decyl-3-methylimidazolium chloride-polyurethane ionic liquid microcapsule; FIG. 2 is DSC curve diagram of ionic liquid-paraffin composite phase-change microcapsule.
Disclosure of Invention
The invention aims to provide a preparation method of an ionic liquid phase-change heat storage material, which utilizes a microcapsule technology to seal phase-change ionic liquid in a microcapsule so as to ensure that the phase-change material is not leaked and the reversibility of a phase-change process is ensured. The phase-change heat storage material prepared by the method can be processed into an automatic temperature regulating material suitable for the fields of medical sanitation, construction, decoration, military facilities and the like.
The ionic liquid phase-change microcapsule consists of an outer wall material and a phase-change heat storage ionic liquid core material which is coated inside.
The outer wall material of the ionic liquid microcapsule is a polymer with acid and alkali resistance, solvent resistance, stable chemical and mechanical properties and good heat transfer property.
The ionic liquid phase change microcapsule core material has the characteristics of good phase change performance, high heat capacity, high heat energy storage density, high heat stability and the like. The combination of these properties can constitute a large number of ionic liquid core materials of varying properties and uses.
The outer wall material of the ionic liquid phase change microcapsule is one or more of phenolic resin, urea resin, polyacrylate, polyurethane, polylactic acid and the like.
The phase change temperature of the core material of the ionic liquid phase change microcapsule is in the range of 0-100 ℃, and the melting phase change enthalpy is more than 60J/g.
The ionic liquid microcapsule core material comprises but is not limited to 1-decyl-3-methyl imidazole chloride, 1-methyl imidazole trifluoromethanesulfonic acid, 1-ethyl-3-methyl imidazole nitrate, 1-hexyl-2, 3-dimethyl imidazole bromide or 1-octyl-3-methyl imidazole tetrafluoroborate.
The ionic liquid core material can be a compound of one, two or more ionic liquids, and also can be a compound of the ionic liquid and paraffin so as to realize the regulation and control of different phase transition temperatures.
The preparation method of the ionic liquid microcapsule comprises the following steps:
(1) dissolving an ionic liquid core material in an organic solvent, and ultrasonically forming a homogeneous and uniform dispersed phase solution, wherein the mass percentage content of the ionic liquid is 5-10%;
(2) preparing a continuous phase solution, wherein the continuous phase solution is an aqueous solution containing wall materials and a surfactant, and the mass percentage content of the surfactant is 0.1-1%;
(3) microencapsulation: mixing and stirring the dispersed phase and the continuous phase to form an oil-in-water or water-in-oil system, adding a polymerization agent to solidify the polymer film material to form a coating on the ionic liquid;
(4) and (3) washing the obtained novel phase-change ionic liquid microcapsule with water for three times, filtering, and drying in the air for 24 hours to obtain the coated ionic liquid phase-change microcapsule.
The preparation method of the ionic liquid phase change microcapsule comprises the following steps of selecting one or more organic solvents from dichloromethane, trichloromethane, ethyl acetate, petroleum ether, cyclohexane and n-hexane; the surfactant is one or more of polyvinyl alcohol, polyoxyethylene, polythioether and alkyl sodium sulfonate; the polymerization agent is one or more of benzoyl peroxide, lauroyl peroxide and azobisisobutyronitrile.
Detailed description of the preferred embodiments
The invention will now be illustrated by the following examples
Example 11-decyl-3-methylchloroimidazole-polyurethane Ionic liquid phase-Change microcapsules
The composition of the microcapsule is as follows: wall material: a polyurethane; ionic liquid: the preparation method of the 1-decyl-3-methyl imidazole chloride comprises the following steps: the method for preparing the microcapsule phase change material by adopting an interfacial polymerization method comprises the following specific steps: firstly, weighing 2.0g of sodium dodecyl benzene sulfonate powder, pouring into 200mL of deionized water, and uniformly stirring, wherein the prepared system is marked as a system I; then, 25g of 1-decyl-3-methylimidazolium chloride and 75g of 2, 4-tolylene diisocyanate were mixed uniformly, and the oil phase system thus prepared was designated as system II. Putting the system I into a shearing emulsifying machine (the rotating speed is 7000r/min), then pouring the system II into the system I for continuous emulsification for 15min, transferring the obtained suspension into a three-neck flask, adding 10mL of 4.5g triethanolamine solution into the system under the condition of continuous stirring, preserving heat at 40 ℃ for 1h, preserving heat at 60 ℃ for reaction for 2h, and preserving heat at 70 ℃ for reaction for 3 h. And finally, cooling and discharging, washing and filtering the obtained microcapsule product, and drying at 60 ℃ for 12 hours to obtain microcapsule powder. The surface topography is shown in the attached figure 1 of the specification.
Example 21 octyl-3-methylimidazolium tetrafluoroborate Ionic liquid-polylactic acid phase Change microcapsules
The composition of the microcapsule is as follows: wall material: polylactic acid; ionic liquid: 1-octyl-3-methylimidazolium tetrafluoroborate. The preparation method comprises the following steps: the preparation method of the polylactic acid coated 1-octyl-3-methylimidazole tetrafluoroborate ionic liquid phase-change microcapsule comprises the steps of firstly preparing 1-6% by mass of polylactic acid and 1-octyl-3-methylimidazole tetrafluoroborate which are added into dichloromethane to form a uniform solution, wherein the solution is an oil phase. Then 0.5-4% by mass of sodium dodecyl sulfate is added to deionized water, and the solution is water phase. And after the two solutions are completely dissolved, mixing the oil phase and the water phase in a ratio of 1:10, uniformly stirring at room temperature and low speed for emulsification reaction, then raising the temperature to 60 ℃ to volatilize dichloromethane to obtain white emulsion, carrying out centrifugal precipitation on the emulsion, and finally carrying out vacuum drying to obtain the 1-octyl-3-methylimidazole tetrafluoroborate ionic liquid phase-change microcapsule.
Example 31-hexyl-2, 3-dimethylimidazolium bromide Ionic liquid-Paraffin composite phase Change microcapsule
The composition of the microcapsule is as follows: wall material: methyl methacrylate; ionic liquid: 1-hexyl-2, 3-dimethylimidazolium bromide.
The preparation method comprises the following steps: preparation of the aqueous phase: 1.5g of emulsifier polyvinylpyrrolidone and 200mL of deionized water were weighed into a three-necked flask and stirred at a low speed at 60 ℃. Preparation of oil phase: 30g of paraffin, 20g of 1-hexyl-2, 3-dimethylimidazolium bromide, 17.8g of monomeric methyl methacrylate, 2.2g of crosslinking agent pentaerythritol tetraacrylate and 0.5g of initiator azobisisobutyronitrile were weighed. Paraffin is put into a 100mL single-neck flask and heated and melted at 60 ℃, then ionic liquid, monomer and cross-linking agent are sequentially added, and finally initiator powder is added to dissolve the ionic liquid, monomer and cross-linking agent. The oil phase was poured into the aqueous phase and was emulsified by mechanical stirring at 1500rpm for 10 min. The temperature is increased to 80 ℃, and the reaction is carried out for 5 hours under the mechanical stirring of 700rpm, so that the polymerization reaction is carried out. And carrying out suction filtration on the obtained sample while the sample is hot, washing the sample with 70 ℃ water and ethanol for three times respectively, and finally putting the obtained product into a 50 ℃ oven to dry the product to constant weight. The DSC phase transition process of the ionic liquid-paraffin composite phase transition microcapsule is shown in figure 2.
Claims (9)
1. The ionic liquid phase-change heat storage microcapsule is characterized by comprising an outer wall material and a phase-change heat storage ionic liquid core material which is coated in the outer wall material.
2. The ionic liquid microcapsule according to claim 1, wherein the outer wall material is a polymer having acid and alkali resistance, solvent resistance, chemical and mechanical stability, and good heat conductivity.
3. The ionic liquid microcapsule according to claim 1, wherein the ionic liquid core material is an ionic liquid having good phase transition properties, high heat capacity and thermal energy storage density, high thermal stability, and the like.
The combination of these properties can constitute a large number of ionic liquid core materials of varying properties and uses.
4. The ionic liquid microcapsule outer layer according to claim 2, wherein the outer layer wall material is one or more of phenolic resin, urea resin, polyacrylate, polyurethane and polylactic acid.
5. The ionic liquid microcapsule according to claim 3, wherein the ionic liquid core material comprises: the melting phase transition temperature is in the range of 0-100 ℃, and the melting phase transition enthalpy is more than 60J/g.
6. The ionic liquid microcapsule according to claim 3, wherein the ionic liquid core material comprises but is not limited to 1-decyl-3-methylimidazolium chloride, 1-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium nitrate, 1-hexyl-2, 3-dimethylimidazolium bromide, or 1-octyl-3-methylimidazolium tetrafluoroborate.
7. The ionic liquid microcapsule according to claim 3, wherein the ionic liquid core material is characterized in that the ionic liquid phase-change material can be a compound of one, two or more ionic liquids, or a compound of an ionic liquid and paraffin, so as to realize the regulation and control of different phase-change temperatures.
8. The preparation method of the ionic liquid microcapsule comprises the following steps:
(1) dissolving an ionic liquid core material in an organic solvent, and performing ultrasonic treatment to form a uniform dispersed phase solution, wherein the mass percentage content of the ionic liquid is 5-10%;
(2) preparing a continuous phase solution, wherein the continuous phase solution is an aqueous solution containing wall materials and a surfactant, and the mass percentage content of the surfactant is 0.1-1%;
(3) microencapsulation: mixing and stirring the dispersed phase and the continuous phase to form an oil-in-water or water-in-oil system, and adding a polymerization agent to solidify the high polymer material to form a coating on the ionic liquid;
(4) and washing the obtained microcapsule with water for three times, filtering, and drying in the air for 24 hours to obtain the coated ionic liquid phase-change microcapsule.
9. The method for preparing the ionic liquid phase-change microcapsule according to claim 6, wherein the organic solvent is one or more of dichloromethane, chloroform, ethyl acetate, petroleum ether, cyclohexane and n-hexane; the surfactant is one or more of polyvinyl alcohol, polyoxyethylene, polythioether and alkyl sodium sulfonate;
the polymerization agent is one or more of benzoyl peroxide, lauroyl peroxide and azobisisobutyronitrile.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113893793A (en) * | 2021-10-25 | 2022-01-07 | 浙江大学 | Size-controllable flexible ionic liquid nano microcapsule and preparation method and application thereof |
| CN115260993A (en) * | 2022-06-29 | 2022-11-01 | 东莞理工学院 | MXene stable ionic liquid based phase change emulsion and preparation method thereof |
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| CN101670256A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Preparation method of phase change material microcapsule |
| CN107779173A (en) * | 2017-10-12 | 2018-03-09 | 北京宇田相变储能科技有限公司 | A kind of microcapsules for improving thermal storage performance and combinations thereof formed body |
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- 2021-01-21 CN CN202110085100.9A patent/CN113214795A/en active Pending
Patent Citations (2)
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| CN101670256A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Preparation method of phase change material microcapsule |
| CN107779173A (en) * | 2017-10-12 | 2018-03-09 | 北京宇田相变储能科技有限公司 | A kind of microcapsules for improving thermal storage performance and combinations thereof formed body |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113893793A (en) * | 2021-10-25 | 2022-01-07 | 浙江大学 | Size-controllable flexible ionic liquid nano microcapsule and preparation method and application thereof |
| CN113893793B (en) * | 2021-10-25 | 2022-12-09 | 浙江大学 | Size-controllable flexible ionic liquid nano microcapsule and preparation method and application thereof |
| CN115260993A (en) * | 2022-06-29 | 2022-11-01 | 东莞理工学院 | MXene stable ionic liquid based phase change emulsion and preparation method thereof |
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Application publication date: 20210806 |